Shelf-stable build materials for 3D printing

ABSTRACT

Build materials for 3D printing applications are described herein which, in some embodiments, comprise monomeric species operable for producing articles with high T g  and/or high heat deflection temperature while maintaining shelf stability. In one aspect, a polymerizable liquid comprises at least 20 weight percent isocyanurate polyacrylate; a photoinitiator component; and a crystallization inhibitor component comprising monomeric curable material, oligomeric curable material or mixtures thereof, wherein the polymerizable liquid does not exhibit crystallization over a period of 28 days at a storage temperature of 5-10° C.

RELATED APPLICATION DATA

The present application claims priority pursuant to 35 U.S.C. § 119(e)to U.S. Provisional Patent Application Ser. No. 62/909,024 filed Oct. 1,2019, which is incorporated herein by reference in its entirety.

FIELD

The present invention relates to three-dimensional build materials and,in particular, to shelf-stable polymerizable liquids for printingthree-dimensional articles exhibiting high heat deflection temperatures.

BACKGROUND

3D printers employ build materials, which are also known as inks, toform various 3D objects, articles, or parts in accordance with computergenerated files. In some instances, the build material is solid atambient temperatures and converts to liquid at elevated jettingtemperatures. In other instances, the build material is liquid atambient temperatures.

Build materials can comprise a variety of chemical species. Chemicalspecies included in a build material can be selected according tovarious considerations including, but not limited to, desired chemicaland/or mechanical properties of the printed article and operatingparameters of the 3D printing apparatus. In some cases, articlesexhibiting high glass transition temperature (T₉) and/or high heatdeflection temperature are desired. However, monomeric species operableto produce these high temperature properties are often unstable andundergo crystallization or other phase separation processes when storedin the liquid phase.

Moreover, hybrid compositions have been introduced comprising lightcurable components and heat curable components. A significantdisadvantage of hybrid systems is the requirement of multiple processingsteps to provide the final article. The hybrid composition, for example,must undergo light curing and heat curing processes. Additionally, theheat curing step can brown or discolor the article.

SUMMARY

In view of these disadvantages, build materials for 3D printingapplications are described herein which, in some embodiments, comprisemonomeric species operable for producing articles with high T_(g) and/orhigh heat deflection temperature while maintaining shelf stability. Inone aspect, a polymerizable liquid comprises at least 20 weight percentisocyanurate polyacrylate; a photoinitiator component; and acrystallization inhibitor component comprising monomeric curablematerial, oligomeric curable material or mixtures thereof, wherein thepolymerizable liquid does not exhibit crystallization over a period of28 days at a storage temperature of 5-10° C. Weight percent of variouscomponents or ingredients recited herein are based on the total weightof the polymerizable liquid.

In some embodiments, the monomeric curable material comprises aheterocycle having two or more unsaturated substituents. For example,the heterocycle can comprise a polyallylated heterocycle, in someembodiments.

In another aspect, methods of printing three-dimensional articles aredescribed herein. A method comprises providing a polymerizable liquidcomprising at least 20 weight percent isocyanurate polyacrylate; aphotoinitiator component; and a crystallization inhibitor componentcomprising monomeric curable material, oligomeric curable material ormixtures thereof, wherein the polymerizable liquid does not exhibitcrystallization over a period of 28 days at a storage temperature of5-10° C. The polymerizable liquid is cured with light to form thearticle, the article having a post-light curing heat deflectiontemperature of at least 100° C. In some embodiments, the article has apost-light curing heat deflection temperature of at least 200° C. or atleast 250° C. Heat deflection temperatures of printed articles describedherein are determined according to ASTM D648 at a stress of 1.82 MPa. Insome embodiments, the article is formed via a layer-by-layer process,wherein layer formation is administered via deposition and irradiationof a layer of the polymerizable liquid.

These and other embodiments are further described in the followingdetailed description.

DETAILED DESCRIPTION

Embodiments described herein can be understood more readily by referenceto the following detailed description and examples. Elements, apparatusand methods described herein, however, are not limited to the specificembodiments presented in the detailed description and examples. Itshould be recognized that these embodiments are merely illustrative ofthe principles of the present invention. Numerous modifications andadaptations will be readily apparent to those of skill in the artwithout departing from the spirit and scope of the invention.

In addition, all ranges disclosed herein are to be understood toencompass any and all subranges subsumed therein. For example, a statedrange of “1.0 to 10.0” should be considered to include any and allsubranges beginning with a minimum value of 1.0 or more and ending witha maximum value of 10.0 or less, e.g., 1.0 to 5.3, or 4.7 to 10.0, or3.6 to 7.9.

All ranges disclosed herein are also to be considered to include the endpoints of the range, unless expressly stated otherwise. For example, arange of “between 5 and 10” should generally be considered to includethe end points 5 and 10.

Further, when the phrase “up to” is used in connection with an amount orquantity, it is to be understood that the amount is at least adetectable amount or quantity. For example, a material present in anamount “up to” a specified amount can be present from a detectableamount and up to and including the specified amount.

The terms “three-dimensional printing system,” “three-dimensionalprinter,” “printing,” and the like generally describe various solidfreeform fabrication techniques for making three-dimensional articles orobjects by selective deposition, jetting, fused deposition modeling,multijet modeling, and other additive manufacturing techniques now knownin the art or that may be known in the future that use a build materialor ink to fabricate three-dimensional objects.

In one aspect, polymerizable liquids for use in 3D printing applicationsare described herein. The polymerizable liquids, for example, can beemployed in a variety of different 3D printers, such as those based onStereolithography (SLA), Digital Light Processing (DLP), and Multi-JetPrinting (MJP). A polymerizable liquid comprises at least 20 weightpercent isocyanurate polyacrylate; a photoinitiator component; and acrystallization inhibitor component comprising monomeric curablematerial, oligomeric curable material or mixtures thereof, wherein thepolymerizable liquid does not exhibit crystallization over a period of28 days at a storage temperature of 5-10° C.

Turning now to specific components, any isocyanurate polyacrylateconsistent with achieving the objectives described herein can beemployed in the polymerizable liquid. In some embodiments, theisocyanurate comprises at least two acrylate substituents ormethacrylate substituents. The isocyanurate, for example, can comprisethree acrylate substituents or methacrylate substituents. In someembodiments, the isocyanurate polyacrylate is of Formula I:

wherein R¹-R³ are independently selected from the group consisting ofhydrogen and alkyl and m, n, and p are integers independently rangingfrom 1 to 10.

In some embodiments, the isocyanurate polyacrylate is present in anamount of at least 30 weight percent or at least 40 weight percent,based on total weight of the polymerizable liquid. The isocyanuratepolyacrylate can also be present in an amount of 30-60 weight percent,based on total weight percent of the polymerizable liquid.

As described herein, the crystallization inhibitor component comprises amonomeric curable material, an oligomeric curable material, or mixturesthereof. A curable material, for reference purposes herein, comprises achemical species that includes one or more curable or polymerizablemoieties. A “polymerizable moiety,” for reference purposes herein,comprises a moiety that can be polymerized or cured to provide a printed3D article or object. Such polymerizing or curing can be carried out inany manner not inconsistent with the objectives of the presentdisclosure. In some embodiments, for example, polymerizing or curingcomprises irradiating a polymerizable or curable material withelectromagnetic radiation having sufficient energy to initiate apolymerization or cross-linking reaction. For instance, in some cases,ultraviolet (UV) radiation can be used. Thus, in some instances, apolymerizable moiety comprises a photo-polymerizable or photo-curablemoiety, such as a UV-polymerizable moiety. In some embodiments, acurable material described herein is photo-polymerizable orphoto-curable at wavelengths ranging from about 300 nm to about 400 nmor from about 320 nm to about 380 nm. Alternatively, in other instances,a curable material is photo-polymerizable at visible wavelengths of theelectromagnetic spectrum.

Moreover, a polymerization reaction, in some cases, comprises a freeradical polymerization reaction, such as that between points ofunsaturation, including points of ethylenic unsaturation. Otherpolymerization reactions may also be used. As understood by one ofordinary skill in the art, a polymerization reaction used to polymerizeor cure a curable material described herein can comprise a reaction of aplurality of “monomers” or chemical species having one or morefunctional groups or moieties that can react with one another to formone or more covalent bonds.

One non-limiting example of a polymerizable moiety of a curable materialdescribed herein is an ethylenically unsaturated moiety, such as a vinylmoiety, allyl moiety, or (meth)acrylate moiety, where the term“(meth)acrylate” includes acrylate or methacrylate or a mixture orcombination thereof.

Additionally, a monomeric curable material and/or an oligomeric curablematerial described herein can comprise a monofunctional, difunctional,trifunctional, tetrafunctional, pentafunctional, or higher functionalcurable species. A “monofunctional” curable species, for referencepurposes herein, comprises a chemical species that includes one curableor polymerizable moiety. Similarly, a “difunctional” curable speciescomprises a chemical species that includes two curable or polymerizablemoieties; a “trifunctional” curable species comprises a chemical speciesthat includes three curable or polymerizable moieties; a“tetrafunctional” curable species comprises a chemical species thatincludes four curable or polymerizable moieties; and a “pentafunctional”curable species comprises a chemical species that includes five curableor polymerizable moieties. Thus, in some embodiments, a monofunctionalcurable material comprises a mono(meth)acrylate, a difunctional curablematerial comprises a di(meth)acrylate, a trifunctional curable materialcomprises a tri(meth)acrylate, a tetrafunctional curable materialcomprises a tetra(meth)acrylate, and a pentafunctional curable comprisesa penta(meth)acrylate. Other monofunctional, difunctional,trifunctional, tetrafunctional, and pentafunctional curable materialsmay also be used.

Any monomeric curable material or combination of monomeric curablematerials not inconsistent with the objectives of the present disclosuremay be used. In some embodiments, a monomeric curable material of apolymerizable liquid described herein comprises one or more species ofacrylates and/or (meth)acrylates, such as one or more monofunctional,difunctional, trifunctional, tetrafunctional acrylates or(meth)acrylates, and/or pentafunctional (meth)acrylates. In someembodiments, for instance, a monomeric curable material comprises methyl(meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl(meth)acrylate, isobutyl (meth)acrylate, n-hexyl (meth)acrylate,2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, n-decyl(meth)acrylate, n-dodecyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate,2- or 3-hydroxypropyl (meth)acrylate, 2-methoxyethyl (meth)acrylate,2-ethoxyethyl (meth)acrylate, 2- or 3-ethoxypropyl (meth)acrylate,tetrahydrofurfuryl methacrylate, isobornyl acrylate, isobornyl(meth)acrylate, acryloyl morpholine, isobornyl acrylate, isobornylmethacrylate, 2-(2-ethoxyethoxy)ethyl acrylate, cyclohexyl methacrylate,2-phenoxyethyl acrylate, glycidyl acrylate, isodecyl acrylate,2-phenoxyethyl (meth)acrylate, lauryl methacrylate, or a combinationthereof. In some embodiments, a monomeric curable material comprises oneor more of allyl acrylate, allyl methacrylate, triethylene glycoldi(meth)acrylate, tricyclodecane dimethanol diacrylate, and cyclohexanedimethanol diacrylate. Additionally, in some cases, a monomeric curablematerial comprises diacrylate and/or dimethacrylate esters of aliphatic,cycloaliphatic or aromatic diols, including 1,3- or 1,4-butanediol,neopentyl glycol, 1,6-hexanediol, diethylene glycol, triethylene glycol,tetraethylene glycol, tripropylene glycol,1,4-dihydroxymethylcyclohexane, 2,2-bis(4-hydroxycyclohexyl)propane orbis(4-hydroxycyclohexyl)methane, hydroquinone, 4,4′-dihydroxybiphenyl,bisphenol A, bisphenol F, or bisphenol S. A monomeric curable materialdescribed herein may also comprise 1,1-trimethylolpropanetri(meth)acrylate, pentaerythritol monohydroxy tri(meth)acrylate,dipentaerythritol monohydroxy penta(meth)acrylate, and/orbis(trimethylolpropane) tetra(meth)acrylate. Further, in some cases, amonomeric curable material can comprise an ethoxylated or propoxylatedspecies, such as ethoxylated or propoxylated neopentyl glycol,ethoxylated or propoxylated bisphenol A, ethoxylated or propoxylatedbisphenol F, ethoxylated or propoxylated bisphenol S, ethoxylated orpropoxylated 1,1,1-trimethylolpropanetri(meth)acrylate, or ethoxylatedor propoxylated glycerol tri(meth)acrylate. In some cases, a monomericcurable material comprises a cycloaliphatic epoxy or N-vinylpyrrolidone.

Additional non-limiting examples of commercially available monomericcurable materials useful in some embodiments described herein includethe following: isobornyl acrylate (IBOA), commercially available fromSARTOMER under the trade name SR 506; isobornyl methacrylate,commercially available from SARTOMER under the trade name SR 432A;triethylene glycol diacrylate, commercially available from SARTOMERunder the trade name SR 272; triethylene glycol dimethacrylate,commercially available from SARTOMER under the trade name SR 205;tricyclodecane dimethanol diacrylate, commercially available fromSARTOMER under the trade name SR 833S; 2-phenoxyethyl acrylate,commercially available from SARTOMER under the trade name SR 339;ethoxylated (3 mole) bisphenol A diacrylate, commercially available fromSARTOMER under the trade name SR 349; a cyclic monofunctional acrylate,commercially available by RAHN USA Corp. under the trade name GENOMER1120; and dipentaerythritol pentaacrylate, commercially available fromSARTOMER under the trade name SR 399 LV. Other commercially availablemonomeric curable materials may also be used.

The monomeric curable material, in some embodiments, is selected fromthe group consisting of aliphatic diacrylates, aliphaticdimethacrylates, cycloalkyl diacrylates, isobornyl acrylate, isobornylmethacrylate, and mixtures thereof.

The monomeric curable material can be present in the polymerizableliquid in any amount not inconsistent with the objectives describedherein. In some embodiments, the monomeric curable material is presentin an amount of 1-60 weight percent, based on total weight of thepolymerizable liquid. The monomeric curable material may also be presentin an amount of 5-50 weight percent or 20-40 weight percent, based ontotal weight of the polymerizable liquid.

In some embodiments, the monomeric curable material comprises aheterocycle comprising two or more unsaturated substituents. Thesubstituted heterocycle, for example, can comprise three unsaturatedsubstituents. The heterocycle can be polyallylated, in some embodiments.In being polyallylated, the heterocycle comprises two of more allylsubstituents. For example, a polyallylated heterocycle can comprise apolyallyl isocyanurate. Alternatively, a heterocycle comprising two ormore unsaturated substituents can be of Formula II:

wherein R⁴-R⁶ are independently selected from the group consisting ofhydrogen and alkyl and m, n, and p are integers independently rangingfrom 1 to 10.

The heterocycle comprising two or more unsaturated substituents,including the heterocycle of Formula II, can be present in thepolymerizable liquid in any amount not inconsistent with the objectivesdescribed herein. In some embodiments, the heterocycle is present in anamount of 5-30 weight percent, based on total weight of thepolymerizable liquid.

In some embodiments, a ratio of the isocyanurate polyacrylate to theheterocycle comprising two or more unsaturated substituents is 1:4 to4:1 or 1:3 to 3:1. The ratio of isocyanurate polyacrylate to theheterocycle comprising two or more unsaturated substituents, forexample, can be about 1:1.

The crystallization inhibitor, in some embodiments, comprises anoligomeric curable material. The oligomeric curable material can be soleingredient of the crystallization inhibitor component or can be in amixture with the monomeric curable material. In general, any oligomericcurable material not inconsistent with the objectives of the presentdisclosure may be used in an ink described herein. In some embodiments,the oligomeric curable material comprises a diacrylate and/ordimethacrylate of esters of aliphatic, cycloaliphatic or aromatic diols,including 1,3- or 1,4-butanediol, neopentyl glycol, 1,6-hexanediol,diethylene glycol, triethylene glycol, tetraethylene glycol,polyethylene glycol, tripropylene glycol, ethoxylated or propoxylatedneopentyl glycol, 1,4-dihydroxymethylcyclohexane,2,2-bis(4-hydroxycyclohexyl)propane or bis(4-hydroxycyclohexyl)methane,hydroquinone, 4,4′-dihydroxybiphenyl, bisphenol A, bisphenol F,bisphenol S, ethoxylated or propoxylated bisphenol A, ethoxylated orpropoxylated bisphenol F or ethoxylated or propoxylated bisphenol S. Anoligomeric curable material can comprise urethane diacrylate, urethanedimethacrylate, aliphatic urethane diacrylate, aliphatic urethanedimethacrylate, polyester diacrylate, polyester dimethacrylate, ormixtures thereof. Some non-limiting commercially available oligomericmaterials include BOMAR BR-952 from DYMAX, CN1964 from SARTOMER, Genomer4247 from RAHN USA, and/or oligomeric materials under the EBECRYL® tradedesignation from ALLNEX, such as EBECRYL® 5781, 5850, 7320 and/or 4859.

Oligomeric curable material of the crystallization inhibitor can bepresent in the polymerizable liquid in any amount not inconsistent withthe objectives described herein. In some embodiments, for example,oligomeric curable material is present in an amount of 5-50 weightpercent or 10-40 weight percent, based on total weight of thepolymerizable liquid. In some embodiments, oligomeric curable is presentin an amount of 0-50 weight percent or 0-40 weight percent, based ontotal weight of the polymerizable liquid.

Polymerizable liquids described herein also comprise a photoinitiatorcomponent for initiating polymerization or curing of the liquid. Anyphotoinitiator not inconsistent with the objectives of the presentdisclosure can be used. In some embodiments, a photoinitiator comprisesan alpha-cleavage type (unimolecular decomposition process)photoinitiator or a hydrogen abstraction photosensitizer-tertiary aminesynergist, operable to absorb light preferably between about 250 nm andabout 420 nm or between about 300 nm and about 385 nm, to yield freeradical(s).

Examples of alpha cleavage photoinitiators are Irgacure 184 (CAS947-19-3), Irgacure 369 (CAS 119313-12-1), and Omnirad (Irgacure) 819(CAS 162881-26-7). An example of a photosensitizer-amine combination isDarocur BP (CAS 119-61-9) with diethylaminoethylmethacrylate.

In addition, in some instances, suitable photoinitiators comprisebenzoins, including benzoin, benzoin ethers, such as benzoin methylether, benzoin ethyl ether and benzoin isopropyl ether, benzoin phenylether and benzoin acetate, acetophenones, including acetophenone,2,2-dimethoxyacetophenone and 1,1-dichloroacetophenone, benzil, benzilketals, such as benzil dimethyl ketal and benzil diethyl ketal,anthraquinones, including 2-methylanthraquinone, 2-ethylanthraquinone,2-tert-butylanthraquinone, 1-chloroanthraquinone and2-amylanthraquinone, triphenylphosphine, benzoylphosphine oxides, forexample 2,4,6-trimethylbenzoyldiphenylphosphine oxide (Lucirin TPO),benzophenones, such as benzophenone and4,4′-bis(N,N′-dimethylamino)benzophenone, thioxanthones and xanthones,acridine derivatives, phenazine derivatives, quinoxaline derivatives or1-phenyl-1,2-propanedione, 2-O-benzoyl oxime, 1-aminophenyl ketones or1-hydroxyphenyl ketones, such as 1-hydroxycyclohexyl phenyl ketone,phenyl 1-hydroxyisopropyl ketone and 4-isopropylphenyl1-hydroxyisopropyl ketone.

Suitable photoinitiators can also comprise those operable for use with aHeCd laser radiation source, including acetophenones,2,2-dialkoxybenzophenones and 1-hydroxyphenyl ketones, such as1-hydroxycyclohexyl phenyl ketone or 2-hydroxyisopropyl phenyl ketone(=2-hydroxy-2,2-dimethylacetophenone). Additionally, in some cases,suitable photoinitiators comprise those operable for use with an Arlaser radiation source including benzil ketals, such as benzil dimethylketal. In some embodiments, a photoinitiator comprises anα-hydroxyphenyl ketone, benzil dimethyl ketal or2,4,6-trimethylbenzoyldiphenylphosphine oxide or a mixture thereof.

Another class of suitable photoinitiators, in some instances, comprisesionic dye-counter ion compounds capable of absorbing actinic radiationand generating free radicals for polymerization initiation. In someembodiments, polymerizable liquids containing ionic dye-counter ioncompounds can be polymerized upon exposure to visible light within theadjustable wavelength range of about 400 nm to about 700 nm. Ionicdye-counter ion compounds and their mode of operation are disclosed inEP-A-0 223 587 and U.S. Pat. Nos. 4,751,102; 4,772,530; and 4,772,541.

A photoinitiator can be present in a polymerizable liquid describedherein in any amount not inconsistent with the objectives of the presentdisclosure. In some embodiments, a photoinitiator is present in anamount of up to about 5 wt. %, based on the total weight of thepolymerizable liquid. In some cases, a photoinitiator is present in anamount ranging from about 0.1 wt. % to about 5 wt. %.

Moreover, in some embodiments, a polymerizable liquid described hereincan further comprise one or more sensitizers. A sensitizer can be addedto increase the effectiveness of one or more photoinitiators that mayalso be present. Any sensitizer not inconsistent with the objectives ofthe present disclosure may be used. In some cases, a sensitizercomprises isopropylthioxanthone (ITX) or 2-chlorothioxanthone (CTX).

A sensitizer can be present in the polymerizable liquid in any amountnot inconsistent with the objectives of the present disclosure. In someembodiments, a sensitizer is present in an amount ranging from about 0.1wt. % to about 2 wt. % or from about 0.5 wt. % to about 1 wt. %, basedon the total weight of the polymerizable liquid.

Polymerizable liquids described herein can further comprise one or moreadditional additives including, but not limited, to pigments, lightstabilizers and/or UV absorbers. In some embodiments, for example, apolymerizable liquid comprises curcumin and/or derivatives and analoguesthereof. Pigments, lights stabilizers and/or UV absorbers can generallybe present in individual amounts less than 2 weight percent or less than1 weight percent, based on total weight of the polymerizable liquid.

As described herein, the polymerizable liquid does not exhibitcrystallization over a period of 28 days at a storage temperature of5-10° C. Crystallization of a polymerizable liquid or absence thereof isdetermined according to the following protocol. A minimum of 10 g ofpolymerizable liquid is placed in an open container for exposure to theambient environment for seeding with impurities and/or particles, suchas dust. The seeded polymerizable liquid is transferred to a 20 mlscintillation vial formed of clear glass. A 35 mm×12 mm strip of brownhigh density polyethylene (HDPE) cut from a Nalgene bottle is placed inthe scintillation vial with the seeded polymerizable liquid. The loadedscintillation vial is then placed in a refrigerator having a stabletemperature of 5-10° C. The polymerizable liquid in the scintillationvial is checked for crystal formation at regular intervals over the 28day period. Crystal formation visible to the eye indicates thepolymerizable liquid fails the test and does not meet the requirement ofno crystallization over a period of 28 days at a storage temperature of5-10° C.

In another aspect, methods of printing three-dimensional articles aredescribed herein. A method comprises providing a polymerizable liquidcomprising at least 20 weight percent isocyanurate polyacrylate; aphotoinitiator component; and a crystallization inhibitor componentcomprising monomeric curable material, oligomeric curable material ormixtures thereof, wherein the polymerizable liquid does not exhibitcrystallization over a period of 28 days at a storage temperature of5-10° C.

Components of the polymerizable liquid employed in methods describedherein can comprise any composition and/or properties describedhereinabove. Additionally, the components can be present in thepolymerizable liquid in any amount described hereinabove. Theisocyanurate polyacrylate, for example, can be present in an amount of30-60 weight percent, based total weight of the polymerizable liquid, insome embodiments.

The polymerizable liquid is cured with light to form the article. Thelight curing process can comprise one or multiple steps. In someembodiments, the polymerizable liquid is initially exposed to asufficient amount of light required to convert the liquid into a softsolid. The soft solid is a green cured state of the article. Additionalphotoreaction is required to complete the polymerization process andobtain the full mechanical strength of the article and achieve othermaterial properties. This additional photoreaction can be completed byplacing the green cured article in a light chamber and providingsufficient time, temperature, and light intensity at the correctwavelengths to complete the polymerization process. As used herein, theterm “post-light curing” refers to the state of the article aftercompletion of the full light initiated polymerization process.Therefore, a post-light cured article has not been subjected to furthernon-light induced polymerization processes, such as thermal curing.

Articles formed according to methods described herein can have apost-light curing heat deflection temperature of at least 100° C. Insome embodiments, the article has a post-light curing heat deflectiontemperature of at least 200° C. or at least 250° C. The article, in someembodiments, can have a post-light curing heat deflection temperatureselected from Table I.

TABLE 1 Printed Article Heat Deflection Temp. (° C.) 140-250 190-250215-250 >250 ≥300

In corresponding to post-light cured articles, the heat deflectionvalues recited herein are achieved without one or more additional steps,such as thermal curing. Accordingly, articles having heat deflectionvalues described herein can be produced via light curing alone, therebysaving cost and time of additional processing steps, including heatcuring.

In addition to high heat deflection temperatures, the article printedaccording to methods described herein can have desirable storage modulusat high temperatures. In some embodiments, the article has a storagemodulus of at least 1500 MPa at 200° C. Moreover, the article can have astorage modulus greater than 1000 MPa at 250° C.

In some embodiments, the article is formed via a layer-by-layer process,wherein layer formation is administered via deposition and irradiationof a layer of the polymerizable liquid.

Layers of polymerizable liquids can be deposited according to an imageof the 3D article in a computer readable format during formation of thethree-dimensional article. The polymerizable liquid can be depositedaccording to preselected computer aided design (CAD) parameters.Moreover, in some cases, one or more layers of the polymerizable liquiddescribed herein has a thickness of about 10 μm to about 100 μm, about10 μm to about 80 μm, about 10 μm to about 50 μm, about 20 μm to about100 μm, about 20 μm to about 80 μm, or about 20 μm to about 40 μm. Otherthicknesses are also possible.

Additionally, it is to be understood that methods of printing a 3Darticle described herein can include so-called “multi-jet” or“stereolithography” 3D printing methods. For example, in some instances,a multi-jet method of printing a 3D article comprises selectivelydepositing layers of a polymerizable liquid described herein onto asubstrate, such as a build pad of a 3D printing system. In addition, insome embodiments, a method described herein further comprises supportingat least one of the layers of the polymerizable liquid with a supportmaterial. Any support material not inconsistent with the objectives ofthe present disclosure may be used.

It is also possible to form a 3D article from a polymerizable liquiddescribed herein using stereolithography. For example, in some cases, amethod of printing a 3D article comprises retaining the polymerizableliquid in a container and selectively applying energy to thepolymerizable liquid in the container to solidify at least a portion ofa polymerizable liquid, thereby forming a solidified layer that definesa cross-section of the 3D article. Additionally, a method describedherein can further comprise raising or lowering the solidified layer toprovide a new or second layer of polymerizable liquid, followed by againselectively applying energy to the polymerizable liquid in the containerto solidify at least a portion of the new or second polymerizable liquidthat defines a second cross-section of the 3D article. Further, thefirst and second cross-sections of the 3D article can be bonded oradhered to one another in the z-direction (or build directioncorresponding to the direction of raising or lowering recited above) bythe application of the energy for solidifying the polymerizable liquid.Moreover, selectively applying energy to the polymerizable liquid in thecontainer can comprise applying electromagnetic radiation, such as UVand/or visible radiation, having a sufficient energy to initiatepolymerization of the polymerizable material as described herein. Inaddition, in some cases, raising or lowering a solidified layer ofpolymerizable liquid is carried out using an elevator platform disposedin the container of fluid build material. A method described herein canalso comprise planarizing a new layer of polymerizable liquid providedby raising or lowering an elevator platform. Such planarization can becarried out, in some cases, by a wiper or roller.

In another aspect, printed 3D articles are described herein. In someembodiments, a printed 3D article is formed from any of thepolymerizable liquids described herein. 3D articles formed frompolymerizable liquids described herein can have heat deflectiontemperatures and/or storage moduli described above.

These foregoing embodiments are further illustrated in the followingnon-limiting examples.

Examples

Table 2 provides formulations of polymerizable liquids according to someembodiments described herein.

TABLE 2 Chemical Formula 1 Formula 2 Formula 3 Formula 4 Urethane 19-2119-21 29-31 29-31 dimethacrylate Isocyanurate 29-31 29-31 29-31 29-31polyacrylate Cycloalkane 16-18 16-18 25-27 25-27 diacrylate Polyallyl18-20 18-20 — — isocyanurate Isobornyl acrylate 10-12  8-10 10-12  8-10Curcumin — — — — Light Stabilizer — 1-2 — 1-2 UV Absorber — 0.5-1   —0.5-1   Photoinitiator 3 3 3 3

Table 3 provides formulations of polymerizable liquids according to someembodiments described herein.

TABLE 3 Chemical Formula 5 Formula 6 Formula 7 Formula 8 Formula 9Formula 10 Urethane dimethacrylate 19-21 19-21 19-21 19-21 19-21 19-21Isocyanurate polyacrylate 34-36 34-36 29-31 29-31 29-31 33-35Cycloalkane diacrylate 20-22 20-22 16-18 16-18 16-18  8-10 Polyallylisocyanurate 20-22 18-20 27-29 29-31 29-31 32-34 Isobornyl acrylate — —— — — — Curcumin — — — — — 0.005-0.01  Light Stabilizer — 1.5-2  1.5-2 — — — UV Absorber — 0.5-1  0.5-1  — — — Photoinitiator 3 3 3 3 3 3

All patent documents referred to herein are incorporated by reference intheir entireties. Various embodiments of the invention have beendescribed in fulfillment of the various objectives of the invention. Itshould be recognized that these embodiments are merely illustrative ofthe principles of the present invention. Numerous modifications andadaptations thereof will be readily apparent to those skilled in the artwithout departing from the spirit and scope of the invention.

The invention claimed is:
 1. A method of printing a three-dimensionalarticle comprising: providing a polymerizable liquid comprising: atleast 20 weight percent isocyanurate polyacrylate, based on total weightof the polymerizable liquid; a photoinitiator component; and acrystallization inhibitor component comprising monomeric curablematerial, oligomeric curable material, or mixtures thereof, wherein themonomeric curable material comprises a heterocycle, and wherein thepolymerizable liquid does not exhibit crystallization over a period of28 days at a storage temperature of 5-10° C.; and curing thepolymerizable liquid with light to form the article, the article havinga post-light curing heat deflection temperature of at least 100° C.according to ASTM D648 at a stress of 1.82 MPa, wherein the monomericcurable material comprises a heterocycle having two or more unsaturatedsubstituents, wherein the heterocycle is a polyallylated heterocycle,and wherein the polyallylated heterocycle comprises polyallylisocyanurate.
 2. The method of claim 1, wherein the post-light curingheat deflection temperature is at least 140° C.
 3. The method of claim1, wherein the post-light curing heat deflection temperature is at least200° C.
 4. The method of claim 1, wherein the post-light curing heatdeflection temperature is at least 250° C.
 5. The method of claim 1,wherein the post-light curing heat deflection temperature is at least300° C.
 6. The method of claim 1, wherein the polymerizable liquid isprovided in a layer-by-layer process.
 7. The method of claim 1, whereinthe article has a storage modulus greater than 1500 MPa at 200° C. 8.The method of claim 1, wherein the isocyanurate polyacrylate is presentin an amount of 30-60 weight percent.
 9. The method of claim 1, whereina ratio of the isocyanurate polyacrylate to the polyallyl isocyanurateis 1:4 to 4:1.
 10. The method of claim 1, wherein the polyallylisocyanurate is present in an amount of 10-30 weight percent based ontotal weight of the polymerizable liquid.